Synthetic lubricants obtained by the telomerization of unsaturated hydrocarbons with polyoxyalkylene compounds



United States Patent Claims. (Cl. 252-52) This invention relates to a process for the telomerization of low molecular weight a-olefius with polyoxyalkylene compounds, and more particularly to the telomerization of u-olefins such as ethylene with polyoxyalkylene compounds in the presence of a free radical initiator, and to the free-flowing liquid telomers thereby obtained, which have properties adapting them for use as synthetic lubricants alone and in blends with mineral lubricating oils.

In recent years, a number of synthetic (i.e,, not petroleum-derived) lubricants have been made available to meet special needs in the field of lubrication. Such lubricants have considerably improved properties, as compared to mineral lubricating oils derived from petroleum, and these properties have made it quite clear that such synthetic lubricants Will continue to find a wide field of utility in those applications where petroleum-derived lu bricants have not proved completely satisfactory. Polyoxypropylene glycols, polyoxyethylene glycols, and mixed polyoxyalkyleue glycols prepared from mixtures of ethylene oxide and propylene oxide, as well as monoalkyl and dialkyl ethers thereof, have been well accepted commercially as synthetic lubricants. Such materials are being marketed in large volume under the trade name Ucon.

The polyoxyalkylene glycol-derived oils have, in. general, higher viscosity indices than petroleum lubricants, as compared to petroleum oils of similar viscosity, and they also have a lower A.P.l. gravity (higher density) and a lower pour point. Because of their high oxygen content, they can be pyrolyzed with little or no carbon residue, and they also have a high solvent capacity for the resins, gums, sludges and varnishes which are formed in internal combustion engines by oxidative decomposition of petroleum products.

However, these oxygenated materials have, in general, the great disadvantage of only a very limited solubility in petroleum-base lubricants. A few diethers of lower polyoxyalkylene glycols of improved solubility have been made available, but these are more volatile than the corresponding glycols. Polyoxyalkylene glycols derived from the higher allrylene oxides such as polyoxybutylene glycols have a better oil solubility than the polyoxyethylene and polyoxypropylene glycols, but of these only the polyoxybutylene glycols have been made available, and then at a price premium over the more common lower glycols. They have not met the need for a synthetic lubricant of this type which would have a considerable solubility in petroleum lubricants. V

Olefins undergo a reaction known as telomerization which has been described in numerous patents and publications. Large amounts of ethylene and propylene are available from petroleum refinery gases, or are made readily on cracking hydrocarbons. These constitute a good source of cheap raw material for making new products, such as telomers.

Telomerization involves the reaction of the olefin, called a taxogen, with a fragment of another molecule, known ild fih Patented June 15, 1955 as a telogen, and the product of this reaction is called a telorner. The reaction can be defined by the following equation:

RI ()Eb-C 11,11

Telogeu Taxogen Telomer R is a hydrogen or an alkyl, aryl, mixed alkyl aryl, mixed aryl alkyl, or cycloalkyl radical.

Telomers are diderent from copolymers and interpolymers. Copolymers and interpolymers contain a number of each of two or more difierent monomer units in the main polymer chain, whereas the fragments of another molecule (the telogen) in telomers appear as units at the terminal of the main polymer chain. Telomerization differs from simple free radical addition to the double bond of an olefin in that more than one molecule of the olefin appears in the product. The telomerization reaction proceeds in the presence of a free radical initiator which removes an active hydrogen from the telogen. The resulting radical initiates the telomerization by adding to the double bond of the olefin.

In the process of the invention, improved synthetic lubricants and lubricant blending agents are provided by telomerizing an er-olefin taxogen with a polyoxyalkylene compound telogen in the presence of a free radical initiator for the telomerization. The product is a free-flowing liquid olefin telomer having a molecular weight below 10,000, and preferably below 2000, containing oxyalkylene units attached to a polymeric olefin-derived hydrocarbon unit.

The preferred telomeric products of the invention are viscous liquids or oils having a viscosity of not over 2000 S.S.U. at F., and preferably not over 1000 S.S.U. at 100 F. (approximately an SAE No. 50 lubricating oil).

These telomers are intended to be used as a lubricant per se, or as a lubricant base for a lubricating oil in blends with other lubricants, or with lubricant additives. In such blends, they function as lubricants, and do not act as viscosity index improvers, or pour point improvers, nor do they have surface active properties. In short, they are lubricants, and not lubricant additives.

They can be prepared to be compatible with mineral oil at a rather high level of solubility, or to be relatively insoluble in mineral oil, depending upon the proportion of carbon to oxygen, i.e., of oxyalkylene units to polyolefinic hydrocarbon units, in the molecule. In many cases, the solubility of the telomer in the oil decreases with decreasing concentration in the oil; this is the result of the material being a better solvent for the mineral oil than the mineral oil is for the telomer.

The telogen is a polyoxyalkylene compound having at least one tertiary hydrogen on a carbon atom adjacent to an ether oxygen atom, and can be defined by the following general formula:

where R and R are hydrogen or alkyl, aryl, mixed aryl alkyl, mixed alkyl aryl, or cycloalkyl radicals having from one to twenty-four carbon atoms, R R and R are hydrogen or alkyl, aryl, mixed aryl alkyl, mixed alkyl aryl and cycloheptyl.

'amylene, -1,3-amylene, 1,4-amylene, 1,5-amylene, ,amylene, 2,4-amylene, 1,2-hexylene,

or cycloalkyl radicals having from one to eight carbon 7 atoms, x is the number of units in the oxyalkylene unit, and ranges from to 10, and m is a number representing the number of repeating oxyalkylene units in the chain, and ranges fromabout to several thousand, usually not over 10,000, and preferably below 5000. It will be understood that the repeating oxyalkylene'units can be complex mixtures of such units,

such mixtures being obtainable from mixtures of alkylene oxides.

These compounds are polyoxyalkylene glycols, or monoor diethers of polyoxyalkylene glycols, depending upon R and'R All are inclusively referred to herein as polyoxyalkylene compounds, for simplicity of terminology, and the residues thereof in the telomer are referred to as polyoxya-lkylene units, whether glycols, monoglycol ethers or diethers.

Typical R R and R radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-amylyisoamyl, tertiary amyl, n-hexyl, isohexyl, phenyl, xylyl, benzyl, fi-phenylethyl, a-phenylethyl, tolyl, ethylphenyl, cyclohexyl, methylcyclohexyl, cyclopentyl R and R can be any of the above and, in addition,

2-ethylhexyl, n-heptyl, tert-hepty-l, n-octyl, isooctyl, tertoctyl, n-nonyl, tert-nonyl, n-decyl, and tert-decyl.

Typical aliphatic radicals are ethylene, 1,2-propylene, l,3 -p ropylene, 1,2-

butylene, 1,3-butylene, '1,4-butylene', 2,3-butylene,

1,2-octylene, octylene, 1,8-octylene and l,2-heptylene.'

Mixed aliphatic aromatic radicals and aliphatic cycloaliphatic radicals analogous to these will be obtained by substituting a ryl and cycloalkyl and mixed alkyl aryl and aryl alkyl radicals for hydrogen in any of these radicals.

A-s exemplary of polyoxyalkylen'e' compound taxogens there can be mentioned polyoxyethylene'glycols, polyoxy:

l,2-propylene glycols, monomethyl ether of polyoxy-l,2-

fpropylene glycol, diethyl ether of polyoxy-1,2-propylene glycol, dimethyl ether of polyoxyl-l,2-propyiene glycol,

polyoxy-LZ-butylene glycols, polyoxy-2,3-butylene glycols, monobutylene-polyoxy-l,Z-prbpylene glycol, monobutyl ether of polyoxy-l,3-propylene glycohmonoethyl ether of 'polyoxy-l,2-p-ropylene glycol, and the monobutyl ether of polyoxyethylene-oxy-1,3-propylene (121.) glycol.

The higher molecular weight polyoxyalkylene compounds tend to produce viscous products; As the molecuduce more fluid telorners of better pour point. p

The taxogen is an unsaturated hydrocarbon having the general formula:

R is hydrogen or an aliphatic, aromatic or cycloali phatic radical having from one to sixteen carbon atoms. These are referred to for convenience herein as a-olefins. Typical R radicals are phenyl, methyl, ethyl, isobutyl,

n-hexyl, n-amyl, 'nbutyl, n-propyl; isopropyl, cyclohexyl, cyclopentyl', ben'zyl, tolyl, xylyl, phenethyl, ethyl'phenyl, .n-decyl, n-dodecyl, n-tetradecyl, and methyl cyclohexyl.

These polyoxyalkylene compound .telog'ens' are be- 11 R5 7 R :(:3l:+:lO:IR rvon=orn Telogen Taxogen (A) H[RCH-(|JH2]m 15 s I I Ri0[ l ]m, -z

R3 R4 x W I Telomer In the above equation, R R R R R x andm are as in II, above, and R" is as in Ill, above. m is the number of moles'of the olefin in the polyolefin hydrocarbon unit A, and m is the number of moles of the oxya kylene unit B, in the telomer molecule. r

The ratio m /m determines mineral oil solubility. .Ge nerally speaking, the lower the 'ratio, the lower the solubility in mineral oil, and vice versa. Oil solubility also can be regarded as determined by the ratio of carbon to oxygen in the molecule, which, as is apparent, is merely another way of expressing the ratio 172 m .7 The above reaction mechanism has been tentatively confirmed by infra-red analysis of the telomeric product. 'When the polyoxyalkylene compound contains two or .more tertiary hydrocarbon reactive sites, the telomeriza tion may occur at any or all such sites, depending upon 40 the reaction conditions, and'the amountsand kinds of olefin and free radical initiator available for the telo- 'merization. r

The taxogen used to produce an oil preferably is a mixture of ethylene with other a-olefins containing at least 50 mole percent (50% of total moles) but not over 90 mole percent of ethylene; a-Glefins higher than ethyl- .ene in molecular weight can be used alone, but react more slowly and produce lower conversions and yields than mixtures thereof withe-thylene. I

The telomers obtained using ethylene alone 'or in amounts of more than mole percent contain as the principal reaction product large. quantities of high molecular weight, high melting solid materials, which are not desired, and are outside of the scope of the invention.

Telomers composed partially or Wholly of higherolefins', such as 'butene-l, penetene-l, 4-methyl' pentene-L,

.3 -methyl hexene-l, hexene-l, heptene-rl, octene-l, -dec ene-l, styrene and S- -menthene, are of lower molecular weight and lower mel'ting'point, and are liquids The 'a-olefins higher than ethylene react more slowly, and less completely, than does ethylene. "The larger the amount of branching, the less the reactivity, also. 'These factors contribute to the formation of an oil. 7 l

In each instance, the inclusion of even asmall amount of higher olefin modifies the nature of the reaction product by lowering the melting or pourpoint; Thus, by appropriate adjustment of the proportion of a mixture of ethylene and higher ct-olefin, and the particular higher q-Olfifin, it is possible to prepare a Wide variety of liquid products, ranging from light fluids to'highly viscous oils. In many cases, cleavage. of the polyoxyalkylene compound may occur at the ether oxygen, and such telomeric products include as a part of their'rnolecule polyoxyh *alkylene" groupshaving a lower average molecular weight 5 than the starting compound. Some telomeric'products have a lower molecular weight than the starting compound, despite the fact that the olefin has reacted with it. This is used to advantage in producing a final liquid product of low molecular weight, from a high molecular weight polyoxyalkylene compound.

The ratio of carbon to oxygen in the telomer determines the solubility in petroleum-derived oils. Generally, the higher the ratio, the more soluble in the oil. The extent of branching and the molecular weight determines its melting or pour point.

Telomers obtained from ethylene with only a small proportion, below about 50 mole percent (50% of total moles of olefin), of a higher (it-Olefin, are generally miscible with solvent-extracted neutral oil stocks at all levels of concentration. In this case, the telomeric products are more hydrocarbon-like because a large proportion of ethylene units react with the oxyalkylene units or" the polyoxyalkylene compound, and m /m is higher; this, of course, increases the compatibility with mineral lubricating oil. The chain modification caused :by the incorporation of the higher a-olefin is such as to keep the pour point low enough for practical use as a lubricant, and prevent the production of a solid or waxy product, as would be the case with pure ethylene alone.

Products from polyoxy-l,2-propylene glycol and olefins containing a ratio of I'm/m which is relatively high (0.55 or more for olefin comprising at least 50% ethylene) are generally completely soluble in mineral lubricating oils. As this ratio is decreased, the products have more limited solubility in mineral lubricating oils and as the ratio becomes relatively low, for example, about 0.3, the products are insoluble in mineral lubricating oils. ucts correspond to polyethers containing more than 67 weight percent of combined carbon, or a carbon to oxygen ratio of greater than 3.08 to l. A similar gradation in solubility with the ratio m /m is observed for other polyoxyallzylene compounds, but of course the ratios at which the limits of oil solubility are reached difier.

The reaction requires a free radical initiator, and this substance can be any of those well known to those skilled in the art as useful in the telomerization of ethylene. It should be sufliciently active to decompose freely into free radicals under the reaction conditions which can be employed. Initiators which lead to excessive cleavage of the polyoxyalkylene compound under the reaction conditions should, however, be avoided.

An initiator is required which is capable of depriving the telogen of its active hydrogen, and starting the series of reactions which leads to the telorner. The energy required to remove this hydrogen is apparently higher than that needed in adding a free radical across the carbon-tocarbon double bond of the olefin. Free radicals are required which are active at the temperatures permissible in telomerization reactions. Furthermore, the telomerization reaction chain is easily interrupted and the reaction halted by conventional free radical inhibitors, and the reactants should be relatively free from such inhibitors.

initiators which may be used include diacyl peroxides uch as diacetyl peroxide, dipropionyl peroxide, dibutyryl peroxide, and dilauroyl peroxide, dialkyl peroxides such as di-tert-butyl peroxide, dihexyl peroxide, di-isopropyl peroxide, di-isobutyl peroxide, di-Z-ethylhexyl peroxide, di-n-butyl peroxide, and diethyl peroxide; terpene peroxides, dicycloaliphatic peroxides such as dicyclohexyl peroxide; perhalogen compounds such as hexachloroethane, and combinations thereof with dialkyl peroxides, organometallic compounds such as tetracthyl lead, tetraphcnyl lead, and azo-N N-compounds such as azobis (isobutyronitrile) and diazoaminobenzene.

Di-tert-butyl peroxide is a preferred free radical initiator for use in this invention, because it shows a minimum tendency toward ether cleavage under most reaction conditions.

The stability of free radical initiators is customarily evaluated in terms of half-life at a stated temperature,

Such prodand the following table compares this for several commercially available free radical initiators:

TABLE I No. Moles Compound Temp. Half of Radical 0.) Life Produced (Hours) Per Pound 1. Tetraethyl Lead 5. 62

2. Lauroyl Peroxide 3. 4 2.27

3. Dicumyl Peroxide 130 1.8 3.34

4. Di-t-butyl Peroxide 6. 4 6. 20

5. Benzoyl Peroxide 85 2.15 3. 74

6. 2,4-Dichlorobeuzoyl Peroxide 2.38

7. Azobisfisobutyronitrile) 80 1. 26 5. 50

In general, the half-lite of the free radical initiator employed at the reaction temperature should be within the range from about 0.25 to about 10 hours, since such initiators have been found to give the best results. By suitable modification of the reaction conditions, however, it is possible to employ free radical initiators whose halilite is outside of this range.

The reaction conditions can be widely varied. The conditions should be such that excessive ether cleavage does not occur. The preferred reaction temperature is estab lished by the temperature at which the free radical initiator decomposes to give a rapid liberation of a substantial amount of free radicals within the above-stated range for half-life For di-tertiary-butyl peroxide, for example, the table shows that the preferred reaction temperatures are within the range from 125 to 160 C. At reaction temperatures below this, because of theslower evolution of free radicals, the reaction time tends to be quite long. Higher temperatures may be wasteful, since the free radical initiator may be decomposed at a higher rate than can be utilized in the telomerization, so that the free radicals will be lost and therefore wasted. in general, for heat-decomposable free radical initiators, reaction temperatures Within the range from 40 to 200 C. are useful.

. a If the boiling point of the unsaturated hydrocarbon is low, it is necessary to operate under pressure.

If the free radical initiator is decomposable by radiation, such as by ultravoilet rays, such radiation can be used, and it may then be unnecessary to heat the reaction mixture above room temperature. AZobi-s(cyclohexane nitrile) and azobis(isobutyronitrile) are initiators of this type, and in fact the latter initiator could be used to carry out a telomerization at temperatures below 0 C.

If the reactants are liquids at the reaction temperature, no solvent is necessary unless dilution is desired to maintain control of the reaction rate. However, a solvent for the unsaturated hydrocarbon will assist in bringing it into contactwith the telogen, and it may be possible because of this facilitation of thereaction to use less olefin in the reaction mixture. A solvent also may be desirable when the telogen is a solid in order to increase the reaction rate.

The solvent should be inert under the telomerization re action conditions. Suitable solvents include benzene, cyclohexane, n-octane and iso-octane. Preferably, the reaction mixture is agitated.

The reaction initially is exothermic, and requires careful control to prevent the temperature from rising so high that free radical initiator decomposition becomes too rapid. As the reaction proceeds, less heat is liberated, and eventually it becomes necessary to heat the reaction mixture in order to bring the reaction to completion.

The reaction'time wili depend upon the initiator and the reactants, the concentrations thereof, and thereaction temperature. It is usually convenient to employ reaction conditions such that the reaction can be complete in less than ten hours, but of course, this is a matter of choice, and reaction times as long as thirteen to fifty hours may not be out of line, depending upon the need.

A high olefinconcentration will yield a higher molecu; lar weight product than will a lower olefin concentration- ,A'lowr temperature has the sameie tfect. At any given pressure level, the average molecular weight ofthe prod- 7 not may be increased by operating at the minimum tem:

perature permitted by the decomposition temperature of the free radical initiator, so as to obtain a slow evolution of free radicals, but such reactions will require along time to complete. The same effect may be obtainable by incorporating an inert diluent which is a good solvent for the unsaturated hydrocarbon. w a i The reaction is easily carried out in conventional pressure equipment. The reactants are introduced in anyconvenient order, and the equipmentbrought to the reaction conditions desired. r The ingredients may be brought together in any order but preferably, the polyoxyalkylene compound, the unsaturated hydrocarbon, and the solvent, if one is employed, are first mixed together and the free radical initiator is then added incrementally. if the unsaturated hydrocarbon is a gas such as ethylene, the reaction vessel 7 may be run at a constant olefin gas pressure throughout the reaction during the addition of the free radical initiator. In this'manner, greater telogen conversions may be obtained togetherrwith the production of telomers of a more uniform average molecular weight distribution.

Usually, successful reactions are noticeably exothermic in the early stages of reaction and cooling is often necessary to control the reaction, especially during this early phase of the reaction. The course of reaction is followed from a drop in olefin pressure; if an initial pressure of 850 p.s.i.g. at C. of ethylene-rich olefin is used, the pres sure during a successful reaction will frequently be decreased to to 50% of its initial value during the course of the reaction. Thefinal reaction product is stripped of volatiles by treating the Warm product with a stream of air at 90100 C; Alternately, the product may be. .1'

stripped of volatiles under a vacuum. The stripped prodnot is then cooled'to 0.20 C. and, if necessary, treated with fuilers earth or preferably bentonite clay in order to. remove the small quantity-of wax usually present;

A continuous reaction is ofparticular interest in a commercial process. This is readily eitected by suitableequip- 'ment which permits continuous blending of the polyoxyalkylene compound with he olefin and free radical initiators, holding them in a pressurized reaction chamber in which they have a dwell time equivalent to that required to complete the reaction, and then drawing them off to a working-up. chamber where the solvent is removed and the residue recovered.

Telomer products are obtainablehaving a wide range,

10f molecular weights which varyaccording to the reactants, reaction conditions and concentration of reactants. The molecular weight can range from as low as 500 up to about. 10,000. The low molecular weight ma- Example 1 Into a Magne-Dash one gallon capacity autoclave provided with means for external heating, with cooling coil 7 'for internal cooling, and a stirrer; were placed 980 g. of

pOlyOXy- LZ-propylene glycol having an average molecular weight of about 2000 and 60 g. of di-ter-tiary-butyl peroxide. The contents .wereflushed with nitrogen to this was then added g. of liquid propene-l to a total pressure of p.s.i.g. at 13 C. of nitrogen plus propylene. 'Ethyle'ne gas was then introduced to a total presure of 150 p.s.i.g. at13 C. The coutentswere slowly heated to 133 C. with agitation, and maintained to 149 C. for an additional five hours. i

The crude liquid telomeric product weighed 1289 g., and represented an olefin conversion of about 58%. The average molecular weight was determined to be 768, using the naphthalene eutectic method. The crude product was air-stripped of volatiles by blowing with air at 90'to 100 C., dew-axed with about one-third its weight of fullers earth, and then filtered to give a clear oil having'a density of 0.948; per ml. at 24 C., and an average molecular weight of 999. The oil by carbon-hydrogen analysis ana lyzed'66.87% carbon, 1l.287% hydrogen, corresponding to theempirical formula C H O(C'H The oil had a viscosity of 51 8 S.S.U. at 100 F. and'76.16 S.S.U. at 210 F. The viscosity index was 128.5

Twenty parts of the oil was diluted withsolvent-exracted neutral lubricating oil stock S.S.U. at 100 F., producing a stable oil solution containing 16% telo-.

mer by weight. This solution was stable on standing.

Upon further dilution with oil, 83% of the original de-' Example 1 was repeated employing a -polyoxy-'1,2-

propylene glycol having a molecular weight of 200. Simi lar results were obtained. 7

V V 'Exizmp Ze 3 V Examplel was repeated employing Ucon oil 50 660, the monobutyl ether of the mixed'polyoxy'alkylene glycol obtained from a 1:1 ratio of ethyleneoxide and 1,3-propylene oxide, having an average molecular weight of about 1700; Similar results were obtained.

Example 4 Into a one gallon capacity Magne-Dash autoclave were placed 980 g. of a polyoxy-1,2-propylene glycol having an average molecular weight of about 2000 and 60 .g. of di-terti-ary-butyl peroxide. The contents were flushed with nitrogen to remove air, and 133 g. of liquid fln-butene-l was added from a reservoir undernitrogen pressure. Then, suflicient ethylene gas was added-to a total gas pressure within the autoclave of 750 psig. at 13 C. The contents were slowly. heated with stirring to 136 C., and then maintained at 136 to 150". C. ;for.

an additional seven hours. The crude product weighed 1290 g., representing an olefin-conversion of about 42%; "and had an experimental average molecular weight of about 830, by the naphthalene eutectic method.

The crude liquid telomeric product'was stripped of amines in a bath'with air at 90400' and then'de-' waxed with bentonite clay and filtered, yielding a clear .oil having a density of 0.952 g. per ml. at 250 C. The oil had an average molecular weight of 1050, and its elemental analysis showed 67.11% carbon, 11.22% hydrogen, corresponding to the empirical formula c3H6 cH2 r1 T The viscosity was 665 S.S.U. at 100 F, 94.85 S.S.U. at

210 F., and the viscosity index was 133.

Fourteen parts of the telomer was diluted with 86' partsby weight of solvent-extracted neutral lubricat ng 9 oil stock 140 S.S.U. at 100 F. The resulting oil solution contained telorner, and was stable on standing. Upon further dilution with oil, 73% of the dewaxed telorner remained insolution, while 27% settled out as .an insoluble or less soluble fraction. A 9.4 weight percent sol-ution of the telon er was stable even at C.

Solubility and solvent extraction studies on the telomer showed that products containing more than 67% combined elemental carbon, i.e., a carbon to oxygen weight ratio greater than 3.08 to 1, were completely compatible with mineral oils.

The telorner oil, alone or in solution in mineral lubicating oil, was useful as a lubricating oil, as a kiln lubricant, as a hydraulic fluid and as a plasticizer for synthetic polymers.

Example 5 Example 4 was repeated employing a polyoxy-1,2-propylene glycol having a molecular weight of 400. Similar results were obtained.

Example 6 Into a Magne-Dash one gallon capacity autoclave were placed 980 g. of polyoxy-l,3-propylene glycol having an average molecular weight of about 2000, and 60 g. of di-tertiary-butyl peroxide, 510 g. of liquid propylene, and sufficient ethylene gas to produce a total initial pressure of 800 p.s.i.g. at 16 C. This mixture was reacted at 276 to 303 F. for ten hours.

The crude liquid telomeric product obtained weighed 1306 g. After stripping oil the volatile material by blowing with air, a clear oil was obtained which had an average molecular weight of 833. Its viscosity at 100 F. was 510.7 S.S.U. and at 210 F. 78.72 S.S.U. The viscosity index was 132.

At a 20 weight percent concentration level of the telorner in solvent-extracted neutral oil, 140 S.S.U. at 100 F., 72% of the product was soluble. The solubility decreased upon further dilution with oil. Solvent extraction of the telorner using a 5050 mixture of methanol and water indicated that 14.5% contained more than 67% carbon, or had a carbon-to-oxygen ratio of greater than 3.08 to 1.

The telorner oil, alone or in solution in mineral lubricating oil, was useful as a lubricating oil, as a kiln lubri- Into a one gallon capacity Magus-Dash autoclave was introduced 980 g. of poly0xy-l,2-propylene glycol having an average molecular weight of 2025, 60 g. of di-tertiarybutyl peroxide, 510 g. of liquid propylene, and sufficient ethylene gas to produce a total initial pressure at 16 C. of S00 p.s.i.g. The resulting mixture was reacted at 278 to 292 F. for -f0ur hours. 1265 g. of crude telomeric product was obtained, having an average molecular weight of 826, and a viscosity at 100 F. of 511.7 S.S.U. and at 210 F. of 81.75 S.S.U. The viscosity index was 135.

This oil was slightly less oil-soluble than that of Example 6, and the oil solubility increased upon dilution with oil. 10% of the telorner was miscible with oil in all proportions.

The telorner oil, alone or in solution in mineral lubricating oil, was useful as a lubricating oil, as -a kiln lubricant, as a hydraulic fluid and as a plasticizer for synthetic polymers.

Example 8 Into a Magoo-Dash one gallon capacity autoclave was introduced 980 g. of polyoxy-1,2-propylene glycol having a molecular weight of 2025, 60 g. of di-tertiary-butyl peroxide, 180 g. liquid propylene, and suficient gaseous ethylene to produce a total initial pressure of 840 p.s.i.g. at 13 C. The mixture was reacted at 290 to 295 F. for four hours.

The crude liquid telorneric product obtained Weighed 1276 g, and had an average molecular weight of 889. Solubility in solvent-extracted neutral lubricating oil stock, 140 S.S.U. at F., was determined. It was found that 82% of the product was soluble, at a concentration level of 17 weight percent. The solubility decreased upon further dilution with oil. 6.6% of the total product was soluble in oil in all proportions.

T he telorner oil, alone or in solution in mineral lubricating oil, was useful as a lubricating oil, as a kiln lubricant, as a hydraulic fluid and as a plasticizer for synthetic polymers.

Example 9 Example 8 was repeated employing'Ucon oil LB 1145, the monobutyl ether of polyoxy-1,3-propylene glycol having a molecular Weight of 3300. Similar results were obtained.

Example 10 Into a 500 ml. capacity Magne-Dash autoclave was introduced g. of poly-oxyl,2-propylene glycol having a molecular weight of 2025, 8.6 g. of di-tertiary-butyl peroxide, 60 g. of liquid propylene, and sufiicient gaseous ethylene to produce an initial total pressure of 820 p.s.i.g. at 18 C. The mixture was reacted at 270 to 332 F. for ten hours.

The crude liquid telomerlc product weighed 184 g., and had an average molecular weight of 757. The viscosity at 100F. was 535 S.S.U., and at 210 F. 80.7 S.S.U. The viscosity index was 132. About 50% of the product was soluble in solvent-extracted neutral lubricating oil stock, 140 S.S.U. at 100 F. at a concentration level of 13.5 Weight percent. The solubility decreased upon further dilution with oil. A small quantity of the total product was miscible with oil in all proportions.

The telorner oil, alone or in solution in mineral lubricating oil, was useful as a lubricating oil, as a kiln lubricant, as a hydraulic fluid and as a plasticizer for synthetic polymers.

The telomers of the invention, as the general formula shows, possess a polyhydrocarbon portion and a polyoxyalkylene compound portion. As a result, they have most attractive properties, both chemical and physical.

The polyhydrocarbon and polyoxyalkylene portions of the telorner together, according to their molecular weight and the extent of branching, control the fluidity of the telorner, which varies from a light liquid or oil through a viscous oil, all of which are tree-flowing. The polyoxyalkylene unit modifies the telorner considerably, imparting to it many of the properties of the polyoxyallrylene compound. The ratio of carbon to oxygen in the telomer determines petroleum oil solubility.

When compared to a mineral lubricating oil, it has a higher temperature stability, a higher viscosity index, a higher density and a lower pour point, and the carbon residue upon pyrolysis is considerably lessened. It also has high solvent power for resins and gums as well as for sludges and varnishes. Unlike the common synthetic oil polyoxyalkylene glycols, it can have quite good solubility in petroleum hydrocarbons because of the polyhydrocarbon portion of the tel'omer.

The telomeric oils of the invention are useful alone or in combination with petroleum-derived fluids such as mineral lubricating oils as lubricants for internal combustion engines, high temperature lubricants in glass and ceramic manufacture, kiln lubricants, lubricants for car bearings, heat transfer fiuids, hydraulic fluids, textile lubricants and other applications where low carbon residue, high lubricity and petroleum oil solubility make them quite attractive. They may be useful as radiator coolants, and in the pre vention or alleviation of the eli ects of carburetor icing and associated phenomena when used as additives in petroleum base fuels such as gasoline. They are useful as plasticizers for synthetic resins with Which they are compatible.

The telorneric glycols are themselves susceptible to ll. 7 many reactions, because of the presence of the hydroxyl groups. They may, for example, be reacted with isocyanates or polyisocyanates such as toluene-2,4-diisocyamate to produce urethane or polyurethane resins.

The following example illustrates this reaction:

' Example 11a The 'telomer of'Example 1 was reacted with an equal molal amount of toluene-2,4-di-isocyanate. This was accomplished by stirring into it 20% .by Weight of methyl morpholine .as a reaction medium and promoter. The toluene-2,4-di-isocyanate was gradually poured intothe mixture with stirring over a period of ten minutes. The

7 :mixture was maintained. with stirring at a temperature of 7 100 C. for one hour, and the temperature then gradually increased over a period of one-half hour to a temperature of 150 C. during which time the methyl morpholine Was removed by vaporization and the reaction product became a resinous mass. At this stage, the resinous mass was molded into a shaped product, and heated.

The polyether glycol telomers .will react with organic acids (or their acid chlorides and acid anhydrides) to form monomeric and polymeric esters, depending upon whether the acid is monoor polycarboxylic. Dicarboxylic acids form linear thermoplastic polymers, and triand higher polycarboxylic acids form cage type or. therm-osetting polymers. These esters contain two ester groups with one or more long chain te'lomeric units. a

The. oil-soluble telomers can be inco'rporated in any a hydrocarbon lubricating stock such as a solvent-extracted or solvent-refined oil, i.e., oils treated in accordance with conventional modern methods of solvent-refining lubricat-' such constituents as aromatic, unsaturated and low vis-' cosity index materials, and these are separated. A clay 'treatment may follow, but While this is desirable, it is not essential" Where necessary, a separate propane or the .oil, but if the telomer oil at a certainproportion becomes a solvent for the petroleum oil, even this is not-alimitation. a This application-is a division of copending application .SerialNo. 838,044, filed September'4,'l9'59, now US. Patent No. 3,137,737. V

We claim: V

1. A lubricant consisting essentially of a mineral lubricating oil and an amount sufficient to improve the lubricating properties of the lubricant of a telomer prepared by the telomerization of at least one d-Olefil]. taxogen selected from the group consisting of alkenes having from two to about ten carbon atoms'and styrene Witli'a polyoxyalkylene compound telogen having at least one active hydrogen atom, on a carbonatom adjacent to another oxygen and having the formula 10 hours, until a free-flowing liquid telomer is obtained having a molecular Weight Withinthe range'from about 500 to about 10,000. V r

2. A lubricant in accordance with claim 1 wherein the polyoxyalkylene compound telogen is a polyoxyethylene like deasphalting treatment may be used in conjunction product. The maximum proportion will usually be deter mined by the solubility of the telomer in the petroleum .telomer is. a cotelomer 'olefin' taxogen.

compound telogen.

'3. A lubricant in accordance with claim'l Whereinthe polyoxyalkylene compound telogen is a polyoxypropylene compound telogen' V i 4. A lubricant in accordance'with claim lwherein the polyoxyalkylene compound telogen is a polyoxybutylene compound telogen. V s

5. A lubricant in accordance with claim 1 wherein the of ethylene and a higher alpha- References Cited by the Examiner UNITED STATES PATENTS DANIEL E. WYMAN, Primary Examiner;

JULIUS GREENWALD, Examiner. 

1. A LUBRICANT CONSISTING ESSENTIALLY OF A MINERAL LUBRICATING OIL AND AN AMOUNT SUFFICIENT TO IMPROVE THE LUBRICATING PROPERTIES OF THE LUBRICANT OF A TELOMER PREPARED BY THE TELOMERIZATION OF AT LEAST ONE A-OLEFIN TAXOGEN SELECTED FROM THE GROUP CONSISTING OF ALKENES HAVING FROM TWO TO ABOUT TEN CARBON ATOMS AND STRYRENE WITH A POLYOXALKYLENE COMPOUND TELOGEN HAVING AT LEAST ONE ACTIVE HYDROGEN ATOM ON A CARBON ATOM ADJACENT TO AN ETHER OXYGEN AND HAVING THE FORMULA 